WO2019151412A1 - インクセット及びインクジェット記録方法 - Google Patents

インクセット及びインクジェット記録方法 Download PDF

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Publication number
WO2019151412A1
WO2019151412A1 PCT/JP2019/003421 JP2019003421W WO2019151412A1 WO 2019151412 A1 WO2019151412 A1 WO 2019151412A1 JP 2019003421 W JP2019003421 W JP 2019003421W WO 2019151412 A1 WO2019151412 A1 WO 2019151412A1
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WIPO (PCT)
Prior art keywords
group
ink composition
mass
heterocyclic
solvent
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Application number
PCT/JP2019/003421
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English (en)
French (fr)
Japanese (ja)
Inventor
章光 配島
義顕 近藤
実央 西村
Original Assignee
富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to EP19748060.1A priority Critical patent/EP3747963B1/de
Priority to JP2019569560A priority patent/JP7010975B2/ja
Priority to CN201980010408.8A priority patent/CN111684026B/zh
Publication of WO2019151412A1 publication Critical patent/WO2019151412A1/ja
Priority to US16/940,832 priority patent/US20200354599A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings

Definitions

  • the present disclosure relates to an ink set and an inkjet recording method.
  • an ink jet recording method a recording method using the ink jet method (hereinafter referred to as an ink jet recording method) is applied to various recording materials. It has been applied in various fields because it can record images.
  • a multicolor image is formed using a plurality of color inks to obtain a desired recorded matter.
  • three colors of yellow ink, magenta ink, and cyan ink are used.
  • four colors obtained by adding black ink to these three colors may be used. is there.
  • a plurality of inks having different shades may be used in the same hue range.
  • six colors using light-colored, for example, light cyan ink and light magenta ink are used.
  • seven colors may be used by adding dark-colored dark yellow ink to these six colors.
  • an ink set in which two or more inks are combined is used for inkjet recording.
  • an ink including a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition as an ink using a dye as a colorant
  • a set can be used to record an image having good light resistance and ozone resistance (see, for example, JP-A-2007-138124).
  • an ink set including a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition and having excellent ink storage stability is disclosed (for example, JP 2012-193330 A). (See publication 2).
  • the ink composition includes a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, each ink composition containing a water-soluble organic solvent having a specific structure, and a water-soluble organic solvent and water.
  • An ink set for ink-jet recording in which the ratio is within a specific range is disclosed (see, for example, JP 2012-188545 A).
  • a recording apparatus for recording using an ink jet method includes a discharge nozzle for discharging an ink composition, and records an image by discharging a desired ink composition from the discharge nozzle according to an image. If the ejection nozzle is clogged and non-ejection occurs, the intended ink is not applied, and the reproducibility of the recorded image may be impaired. For this reason, for example, when the apparatus is started, a discharge operation (so-called dummy discharge) is sometimes performed preliminarily at the time of starting the apparatus so that ink is stably discharged from the discharge nozzle. The ink composition discharged in a dummy is accommodated in an ink disposal unit in the apparatus. In a recording apparatus equipped with a plurality of inks, a plurality of colors of ink are discharged in a dummy manner, so that a plurality of colors of ink are mixed and stored in the ink discarding unit.
  • the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition included in the ink set often contain a dye that is an alkali metal salt.
  • a dye that is an alkali metal salt is widely used for dyes of hues other than yellow dyes because they have good solubility and are difficult to precipitate.
  • yellow dyes often use potassium salts rather than lithium salts because the solubility of potassium salts is relatively high and precipitation in inks is less likely to occur.
  • the potassium element contained in the dye (for example, yellow dye) contained in the ink composition is changed to other dyes (for example, cyan ink).
  • the ink composition tends to increase in viscosity.
  • the viscosity of the ink composition discharged by dummy increases, the ink composition gradually accumulates and accumulates, and may come into contact with a recording medium accommodated or transported in the apparatus.
  • ink stains are generated at the contact portion of the recording medium with the ink composition, that is, the side portion that is the back or end face of the recording medium. Ink stains impair the quality and appearance of recorded matter.
  • JP 2012-188545 A discloses an ink set similar to JP 2007-138124 A and JP 2012-193330 A, but also for the type and amount of the counter ion of the dye. There is no mention, and the amount of solvent used in combination also differs from the scope of the present disclosure.
  • a problem to be solved by an embodiment of the present invention is that ink stains on a recording medium (for example, a sheet of recording paper) (eg, ink stains on a portion other than the recording surface (at least part of the side portion and the back portion)). It is an object of the present invention to provide an ink set in which the occurrence of ink is suppressed. Another problem to be solved by other embodiments of the present invention is that ink stains (for example, at least a part of the side and the back) other than the recording surface of the recording medium (for example, a sheet of recording paper). An object of the present invention is to provide an ink jet recording method in which the occurrence of ink stains is suppressed.
  • a yellow ink composition containing at least one compound selected from the group consisting of a compound represented by the following general formula (Y-1) or the following general formula (Y-2) and a salt thereof;
  • a magenta ink composition containing at least one compound selected from the group consisting of a compound represented by the following general formula (M) or the following general formula (MM) and a salt thereof;
  • a cyan ink composition containing at least one compound selected from the group consisting of a compound represented by the following general formula (C) and a salt thereof;
  • a black ink composition containing at least one compound selected from the group consisting of a compound represented by the following general formula (B) and a salt thereof;
  • Including at least Yellow ink composition, magenta ink composition, cyan ink composition, and a black ink composition contains a total weight with respect to, SP value is a nitrogen atom of 22 MPa 1/2 ⁇ 26 MPa 1/2 for each of the ink compositions
  • 10 mass% to 50 mass% of the solvent C not containing nitrogen atoms having an SP value of 29 MPa 1/2 to 31 MPa 1/2 and a solvent not containing nitrogen atoms having an SP value of 32 MPa 1/2 to 34 MPa 1/2 D contains 5% by mass to 30% by mass and water contains 30% by mass to 60% by mass, respectively.
  • the ratio of the total mass of lithium to the total mass of alkali metals contained in the entire ink in which each of the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition is mixed at an equal mass ratio is It is an ink set which is 70 mass% or more.
  • R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl group Represents a heterocyclic group, a cyano group, an alkoxy group, an amide group, a ureido group, an alkylsulfonylamino group, an arylsulfonylamino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group.
  • G represents an atomic group forming a 5- to 8-membered nitrogen-containing heterocycle
  • M represents a hydrogen atom or a cation.
  • m1 represents an integer of 0 to 3.
  • R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, carbon number A linear or branched aralkyl group having 7 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, a linear or branched alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, C3-C12 cycloalkenyl group, halogen atom, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, amino group, alkyloxy group, aryl
  • each M independently represents a hydrogen atom or a cation.
  • Z 11 represents an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.2 or more.
  • Z 12 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, a heterocyclic group, or an acyl group.
  • R 11 and R 12 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl.
  • R 11 and R 12 do not represent a hydrogen atom at the same time.
  • R 13 , R 14 , b, c, and d are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxy group, carbamoyl Group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group, ureido group, sulfamoyla
  • R 13 and R 11 , or R 11 and R 12 may be bonded to each other to form a 5-membered ring or a 6-membered ring.
  • a and e each independently represent an alkyl group, an alkoxy group, or a halogen atom. When both a and e represent an alkyl group, the total number of carbon atoms in the alkyl group is 3 or more.
  • a and b, or e and d may be bonded to each other to form a ring.
  • Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, or a heterocyclic group.
  • general formula (M) has at least one ionic hydrophilic group.
  • R 1 , R 5 , R 6 , and R 10 each independently represents an alkyl group.
  • R 2 , R 3 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom or Represents a substituent.
  • M 1 and M 2 each independently represents a hydrogen atom, an alkali metal ion or an ammonium ion.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, Alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino Group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyl group, s
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, and Z 1 , Z 2 , At least one of Z 3 and Z 4 has an ionic hydrophilic group as a substituent.
  • l, m, n, p, q1, q2, q3, and q4 each independently represent an integer of 1 or 2.
  • M represents a metal atom or a metal oxide, hydroxide or halide.
  • A represents an aromatic group or a heterocyclic group.
  • X represents a nitrogen atom or ⁇ C (W 1 ) —
  • W 1 represents an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more.
  • V 1 , W, R 43 , and R 44 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, or a carbamoyl group.
  • R 41 and R 42 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group, and R 41 and R 42 do not represent a hydrogen atom at the same time.
  • R 43 and R 41 , or R 41 and R 42 may be bonded to each other to form a 5-membered ring or a 6-membered ring.
  • ⁇ 2> The total mass of lithium with respect to the total mass of alkali metals contained in the entire ink obtained by mixing each of the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition at an equal mass ratio
  • ⁇ 3> The total mass of lithium with respect to the total mass of alkali metals contained in the entire ink obtained by mixing each of the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition at an equal mass ratio
  • the ratio of the mass of lithium to the total mass of alkali metals is 70% by mass or more. It is an ink set as described in any one of ⁇ 3>.
  • the black ink composition is the ink set according to any one of ⁇ 1> to ⁇ 4>, further including a compound represented by the following general formula (BA).
  • a ring, B ring, and C ring each independently represent an aryl group or a heterocyclic group.
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 11 , A 12 , A 13 , A 14 , A 15 , B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 11 , B 12 , B 13 , B 14 , B 15 , B 16 , C 1 , C 2 , C 3 , C 4 , C 11 , C 12 , C 13 , and C 14 are each independently a hydrogen atom or a substitution Represents a group.
  • Q 1 and Q 2 each independently represents a hydrogen atom or a substituent.
  • L 12 represents a divalent linking group.
  • the above-mentioned A 1 to A 5 , A 11 to A 15 , B 1 to B 6 , B 11 to B 16 , C 1 to C 4 , C 11 to C 14 , Q 1 , Q 2 , and L 12 At least one has at least one ionic hydrophilic group.
  • Solvent A is 2-ethyl-1,3-hexanediol
  • Solvent B is 2-pyrrolidone
  • Solvent C is 1,3-butanediol
  • Solvent D is glycerin
  • ⁇ 1> The ink set according to any one of ⁇ 5>.
  • ⁇ 7> Each of the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition has a surfactant content of 0.1 mass relative to the total mass of each ink composition.
  • ⁇ 8> An inkjet recording method for recording an image using the ink set according to any one of ⁇ 1> to ⁇ 7>.
  • the occurrence of ink stains on a recording medium (for example, a sheet of recording paper) (for example, ink stains on portions other than the recording surface (at least a part of the side portion and the back portion)) is suppressed.
  • An ink set is provided.
  • An ink jet recording method in which generation is suppressed is provided.
  • the “back” refers to the surface opposite to the front side (back side) on which recording is performed on the recording medium
  • the “side” connects the front side surface and the back side surface.
  • the end portion refers to an end portion having an area corresponding to the thickness of the recording medium.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • R represents an alkyl group, an aryl group or a heterocyclic group
  • R represents an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted group”.
  • the ink set of the present disclosure includes the following ink compositions having at least four hues, and may further include ink compositions other than the following four hues as necessary.
  • the “ink composition” is also simply referred to as “ink”.
  • Cyan ink composition Ink composition containing at least one compound selected from the group consisting of compounds represented by C) and salts thereof (4) Black ink composition From the group consisting of compounds represented by formula (B) and salts thereof Ink composition containing at least one selected compound
  • the ink composition in the ink set of the present disclosure is not limited to the case where each indicates only a single color, and may include a plurality of colors within the range of each hue system depending on the color shade or hue.
  • a magenta ink composition it may include only a single color magenta ink composition, or may include, for example, two colors of a light magenta ink composition and a dark magenta ink composition.
  • a magenta ink composition for example, those including two colors of a magenta ink composition having a hue close to red and a magenta ink composition having a hue close to pink are included.
  • the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition described above each have an SP value of 22 MPa 1/2 to 26 MPa in addition to the colorant.
  • the solvent A that does not contain 1/2 nitrogen atom (hereinafter also referred to as solvent A) is 0.5 mass% to 5.0 mass% with respect to the total mass of each ink composition, and the SP value is 24 MPa 1 /.
  • Solvent B containing nitrogen atoms of 2 to 29 MPa 1/2 (hereinafter also referred to as solvent B) is 0.1% by mass to 5.0% by mass with respect to the total mass of each ink composition, and the SP value is
  • the solvent C containing 29 MPa 1/2 to 31 MPa 1/2 and not containing nitrogen atoms (hereinafter also referred to as solvent C) is 10% by mass to 50% by mass with respect to the total mass of each ink composition, and the SP value is 32 MPa.
  • the ejected ink composition is accommodated in a waste section.
  • ink compositions of a plurality of colors are mixed.
  • a lithium salt is widely used for a dye contained in an ink composition (for example, a dye contained in an ink composition of a hue other than yellow).
  • Potassium salts are sometimes used as dyes (for example, yellow dyes) due to the fact that they are similarly high and difficult to precipitate in ink.
  • the potassium element contained in the dye is potassium.
  • Substitution with lithium element in dyes other than salt for example, dyes of hues other than yellow (for example, cyan dye, black dye) may lead to thickening of the ink composition.
  • the viscosity of the ink composition discharged by dummy increases, the ink composition gradually accumulates and accumulates in the apparatus and may come into contact with a recording medium accommodated or conveyed in the apparatus.
  • the contact portion between the portion other than the recording surface of the recording medium and the ink composition that is, the side or back of the recording medium corresponding to the thickness, even if the recording surface is not touched. Ink adheres to the part and ink stains occur. Ink stains impair the quality and appearance of recorded matter.
  • each of the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition contains a compound having a structure suitable for each color as a colorant, and an alkali metal
  • the composition contains four types of solvents having different SP values in combination at a specific ratio. Thereby, for example, it is possible to suppress the occurrence of ink stains on a portion other than the recording surface (at least a part of the side portion and the back portion) of the sheet recording medium.
  • the ink set of the present disclosure includes four colors of a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, and each of the four color ink compositions is mixed at an equal mass ratio.
  • the ratio (M Li / M I ) of the total mass (M Li ) of lithium to the total mass (M I ) of alkali metals contained in the entire ink of the ink set is 70% by mass or more.
  • the ratio represented by M Li / M I is 70% by mass or more means that the total amount of lithium metal contained in the yellow ink composition, magenta ink composition, cyan ink composition, and black ink composition (Content ratio) is high, indicating that the thickening phenomenon of the ink composition that is likely to occur when an alkali metal other than lithium (for example, potassium) is mixed is unlikely to occur.
  • the ratio of the total mass of lithium to the total mass of alkali metals contained in the entire ink of the ink set is the same as described above. It is preferably 80% by mass or more, and more preferably 85% by mass or more.
  • components included in each ink composition included in the ink set of the present disclosure will be described.
  • components contained in the yellow ink composition will be described first, and then components contained in the magenta ink composition, the cyan ink composition, and the black ink composition will be described.
  • detailed description of the same components as those contained in the yellow ink composition is omitted.
  • Yellow ink composition is at least selected from the group consisting of a compound represented by formula (Y-1) or formula (Y-2) and a salt thereof as a colorant. Contains one compound, solvent A, solvent B, solvent C, solvent D, and water, and may contain other components such as surfactants and additives as necessary. Good.
  • the solvents (solvents A to D) contained in the yellow ink composition will be described.
  • the numerical value in parentheses described after the compound name represents the SP value (unit: MPa 1/2 ) of the solvent, and the unit is omitted.
  • the SP value in parentheses is a value obtained by rounding off the first decimal place.
  • the SP value (solubility parameter / unit: MPa 1/2 ) of the solvent in the present disclosure is a value represented by the square root of the molecular cohesive energy. F. It can be calculated by the method described in Fedors, Polymer Engineering Science, 14, pp. 147 to 154 (1974), and this numerical value is adopted in the present disclosure.
  • Yellow ink composition contains a solvent A having an SP value does not contain a nitrogen atom of 22 MPa 1/2 ⁇ 26 MPa 1/2
  • the content of the solvent A is, with respect to the total mass of the yellow ink composition, 0.
  • the range is from 5% by mass to 5.0% by mass.
  • the content of the solvent A is set to a range of 0.5% by mass or more.
  • the content of the solvent A is set to 5.0% by mass or less.
  • the content of the solvent A is preferably in the range of 1.0% by mass to 3.0% by mass with respect to the total mass of the yellow ink composition.
  • the SP value of the solvent A is 22 MPa 1/2 or more, it is easy to maintain good solubility of the dye, and it is difficult to cause separation of the dye or precipitation of the dye under a low temperature environment. Further, when the SP value is 26 MPa 1/2 or less, the effect of reducing the surface tension of the ink is high, and the discharge performance is improved.
  • the SP value of the solvent A for the same reason as described above, 24MPa 1/2 ⁇ 25MPa 1/2 is preferred.
  • solvent A examples include 2-ethyl-1,3-hexanediol (25), polyethylene glycol 200 (26), polypropylene glycol 200 (25), GP250 (22), diethylene glycol monobutyl ether (22), triethylene Examples include glycol monomethyl ether (22), triethylene glycol monoethyl ether (22), 2-ethyl-2-butyl-1,3-propanediol (25), and 1,2-hexanediol (24). Of these, 2-ethyl-1,3-hexanediol (25 MPa 1/2 ) is more preferable.
  • the content of the solvent A is 0.5% by mass or more, the effect of reducing the surface tension of the ink is high, and the ejectability is improved. Further, when the content of the solvent A is 5.0% by mass or less, the solubility of the dye is easily maintained, and the precipitation of the dye is effectively suppressed.
  • the content of the solvent A is preferably 1.0% by mass to 3.0% by mass with respect to the total mass of the yellow ink composition.
  • the yellow ink composition contains a solvent B containing a nitrogen atom having an SP value of 24 MPa 1/2 to 29 MPa 1/2 , and the content of the solvent B is about 0. 0 relative to the total mass of the yellow ink composition.
  • the range is from 1% by mass to 5.0% by mass.
  • the content of the solvent B is set to a range of 0.1% by mass or more.
  • the SP value of the solvent B is 24 MPa 1/2 or more, the precipitation of the dye is effectively suppressed. Further, when the SP value of the solvent B is 29 MPa 1/2 or less, the ink ejection stability is improved.
  • the SP value of the solvent B and for the same reason as described above, 25MPa 1/2 ⁇ 26MPa 1/2 is preferred.
  • solvent B examples include 2-pyrrolidone (26), N-methyl-pyrrolidone (24), N-hydroxyethyl-pyrrolidone (29), 2-amino-2-ethyl-1,3-propanediol (28 ), Ethylene urea (29), compound (25) represented by the following structural formula (1) -1, compound (24) represented by the following structural formula (1) -2, and the like.
  • 2-pyrrolidone is more preferable.
  • the content of the solvent B is in the range of 0.1% by mass to 5.0% by mass with respect to the total mass of the yellow ink composition.
  • the content of the solvent B is preferably 0.3% by mass to 3.0% by mass, and preferably 0.5% by mass to 2.0% by mass with respect to the total mass of the yellow ink composition for the same reason as described above. % Is more preferable.
  • the yellow ink composition contains a solvent C that does not contain a nitrogen atom having an SP value of 29 MPa 1/2 to 31 MPa 1/2 , and the content of the solvent C is 10 mass relative to the total mass of the yellow ink composition. % To 50% by mass. Solvent C increases the solubility of the dye most among the solvents A to D. Therefore, when the solvent C is contained, the effect of preventing the precipitation of the dye is great.
  • the solvent C is, SP value serves as dissolution aid of solvent of less than 29 MPa 1/2, especially the ink composition of the "solvent A to SP value does not contain a nitrogen atom of 22 MPa 1/2 ⁇ 26 MPa 1/2" Suppresses separation and precipitation inside. From this viewpoint, the content of the solvent C is set to a range of 10% by mass or more.
  • the solvent C When the SP value of the solvent C is 29 MPa 1/2 or more, the solvent C has a strong function as a solvent aid, and the effect of improving the solubility of the dye is high. Moreover, when SP value is 31 Mpa 1/2 or less, it is advantageous at the solubility point of solvent C itself.
  • the SP value of the solvent from C same reason as described above, the range of 30 MPa 1/2 ⁇ 31 MPa 1/2 is more preferred.
  • solvent C examples include 1,3-butanediol (30), diethylene glycol (31), 1,5-pentanediol (29) and the like. Of these, 1,3-butanediol is more preferable.
  • the content of the solvent C is 10% by mass or more, the solubility of the dye can be effectively increased. Further, when the content of the solvent C is 50% by mass or less, phase separation does not occur in the ink, which is advantageous in terms of liquid stability.
  • the content of the solvent C is preferably 15% by mass to 45% by mass and more preferably 20% by mass to 35% by mass with respect to the total mass of the yellow ink composition for the same reason as described above.
  • the yellow ink composition contains a solvent D that does not contain a nitrogen atom having an SP value of 32 MPa 1/2 to 34 MPa 1/2 , and the content of the solvent D is 5 mass relative to the total mass of the yellow ink composition. % To 30% by mass. Solvent D enhances the moisture retention of the ink composition most among the solvents A to D. Therefore, by containing the solvent D, the ink composition is prevented from drying at the discharge port of the ink jet head and the place where the ink composition discharged by dummy and discarded is stored.
  • the content of the solvent D is set to a range of 5% by mass or more.
  • the SP value of the solvent D is 32 MPa 1/2 or more, the moisturizing effect of the ink composition is high, and drying of the ink composition is suppressed. As a result, precipitation of the dye in the ink composition is suppressed.
  • an SP value of 34 MPa 1/2 or less is advantageous in that the solubility in water is high and the compatibility with the solvents A, B, and C is also high.
  • the SP value of the solvent D is more preferably in the range of 33 MPa 1/2 to 34 MPa 1/2 for the same reason as above.
  • the solvent C examples include glycerin (34), propylene glycol (33), 1,3-propanediol (33), diglycerin (32) and the like. Among these, glycerin is more preferable.
  • the content of the solvent D is 5% by mass or more, the effect of preventing the ink composition from drying is excellent, and the precipitation of the dye in the ink composition is suppressed. Further, when the content is 30% by mass or less, phase separation does not occur in the ink, which is advantageous in terms of liquid stability.
  • the content of the solvent D is preferably 8% by mass to 28% by mass and more preferably 10% by mass to 25% by mass with respect to the total mass of the yellow ink composition for the same reason as described above.
  • the solvent A is, SP value does not contain a nitrogen atom of 24 MPa 1/2 ⁇ 25 MPa 1/2 It is a solvent, and its content is 1.0 mass% to 3.0 mass% with respect to the total mass of the yellow ink composition, and the solvent B has an SP value of 25 MPa 1/2 to 26 MPa 1/2. And a content of 0.5% by mass to 2.0% by mass with respect to the total mass of the yellow ink composition, and the solvent C has an SP value of 30 MPa 1/2. 2 to 31 MPa 1/2 of a solvent not containing nitrogen atoms, and the content is 20 to 30% by mass with respect to the total mass of the yellow ink composition.
  • Solvent D has an SP value of 33 MPa. 1/2 to 34 A solvent not containing a nitrogen atom Pa 1/2, and the content is the total mass of the yellow ink composition is preferably 10 wt% to 25 wt%.
  • preferred solvents in the yellow ink composition are as follows. From the same viewpoint as described above, the solvent A is 2-ethyl-1,3-hexanediol, the solvent B is 2-pyrrolidone, and the solvent C is A preferred embodiment is 1,3-butanediol and the solvent D is glycerin.
  • the yellow ink composition of the present disclosure may further contain a solvent other than the solvents A to D as long as the effects of the ink set of the present disclosure are not significantly impaired.
  • the details and preferred embodiments of the solvent A, the solvent B, the solvent C, and the solvent D are the same not only in the yellow ink composition but also in the magenta ink composition, cyan ink composition, and black ink composition described later. .
  • the water content is 30% by mass to 60% by mass, preferably 40% by mass to 55% by mass. %.
  • the water content is 30% by mass or more, the water-soluble dye can be stably dissolved.
  • compatibility with the solvent A, the solvent B, the solvent C, and the solvent D can be satisfied.
  • the yellow ink composition in the present disclosure is at least one compound selected from the group consisting of a compound represented by formula (Y-1) or formula (Y-2) and a salt thereof (also referred to as a yellow dye). Containing.
  • R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl group Represents a heterocyclic group, a cyano group, an alkoxy group, an amide group, a ureido group, an alkylsulfonylamino group, an arylsulfonylamino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group.
  • R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 may be unsubstituted or substituted with a substituent. The substituent will be described later.
  • R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 and Z 2 include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, Alternatively, a heterocyclic group is preferable, and a hydrogen atom, an alkyl group, an aryl group, a cyano group, or an alkylsulfonyl group is most preferable.
  • R 1 and R 2 are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted total carbon atoms.
  • a heterocyclic group having 4 to 12 carbon atoms is preferable, and further, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, particularly a secondary or tertiary alkyl group is preferable, and a t-butyl group is most preferable. preferable.
  • X 1 and X 2 are preferably a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms.
  • An alkylsulfonyl group having 1 to 12 carbon atoms or a sulfamoyl group having 0 to 12 carbon atoms is more preferable, and a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is further preferable.
  • Y 1 and Y 2 are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total carbon number.
  • a 4 to 12 heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total and / or a branched alkyl group are preferable, and a hydrogen atom or an alkyl group having 1 to 8 is particularly preferable.
  • a hydrogen atom is most preferred.
  • Z 1 and Z 2 include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl A group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, a substituted aryl group or a substituted heterocyclic group is more preferred, and a substituted aryl group is still more preferred.
  • R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms as a substituent, C7-18 linear or branched aralkyl group, C2-12 linear or branched alkenyl group, C2-12 linear or branched alkynyl group, C3-12 cycloalkyl Group having 3 to 12 carbon atoms (the above groups are preferably those having a branched chain for the purpose of improving the solubility of the dye and the stability of the ink, and particularly preferably those having an asymmetric carbon.
  • G represents an atomic group forming a 5- to 8-membered nitrogen-containing heterocycle.
  • Preferred examples of the 5- to 8-membered nitrogen-containing heterocycle in G include S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring.
  • An S-triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is more preferable, and an S-triazine ring is still more preferable.
  • M represents a hydrogen atom or a cation.
  • a cation in M an alkali metal ion, an ammonium ion (NH 4 + ), or a quaternary ammonium ion (NR 4 + ) is preferable, and Li + ion, Na + ion, K + ion, NH 4 + ion, or NR 4 + ions are more preferred.
  • R represents an alkyl group or an aryl group, and is synonymous with the examples of the alkyl group and the aryl group represented by R 1 etc. and Y 1 etc.
  • M is preferably Li + ion, Na + ion, K + ion, or NH 4 + ion, more preferably Li + ion, Na + ion, or K + ion, and most preferably Li + ion.
  • m1 represents an integer of 0 to 3.
  • m1 is preferably 0 to 2.
  • R 1 and R 2 may be the same or different and are a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted group.
  • an unsubstituted heterocyclic group having a total carbon number of 4 to 12 is preferable, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group, or an amino group is more preferable, and a secondary or tertiary alkyl group or amino group is more preferable.
  • X 1 and X 2 may be the same or different, and are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms.
  • a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is still more preferable.
  • (C) Y 1 and Y 2 may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total. Or a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total, a hydrogen atom or a substituted or unsubstituted alkyl group is more preferred, and a hydrogen atom is still more preferred.
  • Z 1 and Z 2 may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted
  • An unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferred, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is more preferred, and a substituted aryl group is still more preferred.
  • a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are substituted with an ionic hydrophilic group (for example, a carboxylate (preferably an alkali metal salt), a sulfonic acid or a sulfonate (preferably an alkali metal). Salts), phosphonic acids or phosphonates (preferably alkali metal salts)) are preferred.
  • an ionic hydrophilic group for example, a carboxylate (preferably an alkali metal salt), a sulfonic acid or a sulfonate (preferably an alkali metal). Salts), phosphonic acids or phosphonates (preferably alkali metal salts) are preferred.
  • (E) G represents an atomic group forming a 5- to 8-membered nitrogen-containing heterocycle, and preferred examples of the 5- to 8-membered nitrogen-containing heterocycle include S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine A ring, a pyridine ring, an imidazole ring, a pyrazole ring, or a pyrrole ring. Among these, an S-triazine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is preferable, and an S-triazine ring is most preferable.
  • m1 represents an integer of 0 to 3.
  • M is preferably a hydrogen atom or a cation, more preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, still more preferably a Li + ion, a Na + ion, a K + ion, or NH 4 +. Ions, most preferably Li + ions.
  • R 1 in the general formula (Y-1), R 2 , Y 1 and Y 2 respectively synonymous
  • the preferred embodiments are also the same.
  • X 1 and X 2 each independently represents a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, a cyano group, or An alkylsulfonyl group having 1 to 12 carbon atoms is preferred.
  • Z 1 and Z 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group.
  • Z 1 and Z 2 are each a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon group having 4 to 12 carbon atoms.
  • a heterocyclic group is preferred, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is more preferred, and a substituted aryl group is still more preferred.
  • the substituents that Z 1 and Z 2 may have are R 1 , R 2 , X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 in General Formula (Y-1). Are the same as the substituents which may have, and the preferred embodiments are also the same.
  • M represents a hydrogen atom or a cation, preferably a hydrogen atom, an alkali metal ion, an ammonium ion, or a quaternary ammonium ion, more preferably a Li + ion, a Na + ion, a K + ion, or an NH 4 + ion. Li + ions are most preferred.
  • the compound when it is preferable that the compounds represented by the general formulas (Y-1) and (Y-1-1) have hydrophilicity, the compound may have two or more ionic hydrophilic groups in the molecule. Preferably, it has 2 to 10 ionic hydrophilic groups, more preferably 3 to 6 ionic hydrophilic groups.
  • a plurality of M each independently represents a hydrogen atom or a cation.
  • Examples of the cation in M include Li + ion, Na + ion, K + ion, and NH 4 + ion.
  • the main component of M is preferably Li + ions, and all M are more preferably Li + ions. Being a main component means occupying 70% by mass or more of all M.
  • the dye M represented by the general formula (Y-2) contained in the ink composition, not the mixed salt is a K + ion. Since all M is a K + ion, in a molecular dispersion state dissolved in an aqueous solution or an ink solution, a carboxy group that is an ionic hydrophilic group or a salt thereof (—CO 2 M) is dissociated to —CO 2.
  • a carboxy group that is an ionic hydrophilic group or a salt thereof (—CO 2 M) is dissociated to —CO 2.
  • the ratio of the mass of lithium to the total mass of alkali metals in the yellow ink composition is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more. 90 mass% or more is especially preferable.
  • the ratio of the mass of lithium is 70% by mass or more, since the content of alkali metal (especially potassium) other than lithium contained in the ink composition is small, when mixed with an ink composition other than the yellow ink composition The thickening phenomenon is effectively suppressed. As a result, it is possible to suppress ink stains on the recording medium caused by the accumulation of the ink composition.
  • the yellow ink composition in the present disclosure includes a surfactant, colloidal silica, a water-soluble polymer agent, an antifoaming agent, a pH adjuster, a preservative, a polymerization inhibitor, and a drying inhibitor.
  • a surfactant colloidal silica
  • a water-soluble polymer agent an antifoaming agent
  • a pH adjuster a preservative
  • a polymerization inhibitor e.g., a preservative
  • a polymerization inhibitor e.g., a drying inhibitor.
  • wetting agents wetting agents
  • anti-fading agents emulsion stabilizers, penetration enhancers, UV absorbers, anti-mold agents, viscosity modifiers, dispersion stabilizers, anti-rust agents, chelating agents, and other other components You may contain.
  • These other components are the same not only in the yellow ink composition but also in the magenta ink composition, cyan ink composition, and black ink composition described later.
  • the yellow ink composition in the present disclosure can contain a surfactant as long as the effects according to the embodiment of the present invention are not impaired.
  • a surfactant By containing the surfactant, it is possible to lower the surface tension and improve the discharge performance.
  • the surfactant is not substantially contained from the viewpoint of avoiding adverse effects caused by containing the surfactant (such as ejection abnormality due to bubbles near the ejection port). Therefore, in the present disclosure, the content of the surfactant in the yellow ink composition is preferably less than 0.1% by mass with respect to the total mass of the ink composition.
  • the content of the surfactant is less than 0.1% by mass relative to the total mass of the ink composition means that the ink composition does not substantially contain a surfactant, that is, It shows that content is a grade which does not express surface active ability.
  • the ink set of the present disclosure does not contain a surfactant and has a low SP value, that is, the above-described “solvent not containing a nitrogen atom having an SP value of 22 to 26”, thereby reducing the surface tension.
  • a composition that lowers and improves dischargeability is employed. This is because the effect of lowering the dynamic surface tension in a short time is greater than that of the surfactant, and the use of the surfactant avoids various adverse effects caused by the easy generation of bubbles. preferable.
  • the surfactant a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used.
  • Anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant Either an agent or a betaine surfactant may be used.
  • nonionic surfactants are preferable, and acetylene glycol derivatives (acetylene glycol surfactants) are more preferable. Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7.
  • -Alkylene oxide adducts of diols As the surfactant, a commercially available product may be used, and examples of the commercially available product include E series (eg, Olphine E1010) manufactured by Nissin Chemical Industry Co., Ltd.
  • the yellow ink composition in the present disclosure may contain colloidal silica.
  • colloidal silica is a colloid composed of fine particles of inorganic oxide containing silicon having an average particle size of several hundred nm or less.
  • Colloidal silica contains silicon dioxide (including hydrates thereof) as a main component, and may contain aluminate (sodium aluminate, potassium aluminate, etc.) as a minor component.
  • colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.
  • the description in paragraphs 0043 to 0050 of JP-A-2011-202117 can be appropriately referred to.
  • the ink composition in the present disclosure may contain an alkali metal silicate salt instead of or in addition to colloidal silica, if necessary.
  • alkali metal silicate reference can be made to the descriptions in paragraphs 0052 to 0056 of JP 2011-202117 A as appropriate.
  • the content of colloidal silica is preferably 0.0001% by mass to 10% by mass, and 0.01% by mass to 3% by mass with respect to the total amount of the ink composition. Is more preferably 0.02% by mass to 0.5% by mass, and particularly preferably 0.03% by mass to 0.3% by mass.
  • the yellow ink composition in the present disclosure may contain a water-soluble polymer compound.
  • the water-soluble polymer compound is not particularly limited, and known water-soluble polymer compounds such as polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, and polyethylene glycol can be used. Further, as the water-soluble polymer compound, a specific polymer compound that may be contained in a treatment liquid described later and water-soluble polymer compounds described in paragraphs 0026 to 0080 of JP2013-001854A are also suitable. is there.
  • the content of the water-soluble polymer compound is preferably 0.0001% by mass to 10% by mass with respect to the total amount of the ink composition, and 0.01 More preferred is from 3% by weight to 3% by weight, still more preferred is from 0.02% by weight to 0.5% by weight, and particularly preferred is from 0.03% by weight to 0.3% by weight.
  • the yellow ink composition in the present disclosure may contain an antifoaming agent.
  • the antifoaming agent include silicone compounds (silicone defoaming agents) and pluronic compounds (pluronic defoaming agents). Among these, silicone antifoaming agents are preferable.
  • silicone-based antifoaming agent a silicone-based antifoaming agent having a polysiloxane structure is preferable. A commercial item can be used as an antifoamer.
  • BYK-012, 017, 021, 022, 024, 025, 038, 094 (above, manufactured by Big Chemie Japan Co., Ltd.), KS-537, KS-604, KM-72F (above, Shin-Etsu Chemical) Kogyo Co., Ltd.), TSA-739 (Momentive Performance Materials Japan GK), Olfin AF104 (Nisshin Chemical Co., Ltd.), and the like.
  • BYK-017, 021, 022, 024, 025, 094, KS-537, KS-604, KM-72F, and TSA-739 which are silicone-based antifoaming agents, are preferable.
  • BYK-024 is most preferred.
  • the content of the antifoaming agent is preferably 0.0001% by mass to 1% by mass, and 0.001% by mass to 0.1 mass% is more preferable.
  • the yellow ink composition in the present disclosure may contain a pH adjuster.
  • the pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the ink composition to be prepared, and can be appropriately selected according to the purpose.
  • alcohol amines eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol
  • alkali metal hydroxides eg, lithium hydroxide, sodium hydroxide, potassium hydroxide) Etc.
  • ammonium hydroxide for example, ammonium hydroxide, quaternary ammonium hydroxide, etc.
  • phosphonium hydroxide alkali metal carbonate and the like.
  • the content of the pH adjuster is preferably such an amount that the pH of the ink composition is 5 to 10 (more preferably 7.0 to 9.5). .
  • the yellow ink composition in the present disclosure may contain an inorganic salt as a pH buffer.
  • an inorganic salt as a pH buffer.
  • the inorganic salt as the pH buffering agent include carbonates and phosphates, and carbonates are preferred from the standpoint of member resistance.
  • the carbonate include potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate and the like. From the viewpoint of not decreasing the solubility of the dye, lithium carbonate or lithium hydrogen carbonate Is particularly preferred.
  • An inorganic salt can be used individually or in combination of 2 or more types.
  • the content of the inorganic salt in the ink composition (the total content in the case of two or more types) is not particularly limited, but the total amount of the ink composition Is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and particularly preferably 0.03% by mass to 0.1% by mass.
  • magenta ink composition in the present disclosure is at least one compound selected from the group consisting of a compound represented by the general formula (M) or the general formula (MM) and a salt thereof (also referred to as a magenta dye). .), Solvent A, solvent B, solvent C, and solvent D, and water, and may further contain other components such as surfactants and additives as necessary.
  • solvent A, the solvent B, the solvent C, the solvent D, water, and other components in the magenta ink composition are the same as those in the above-described yellow ink composition, and preferred embodiments are also the same. Therefore, detailed description in this column is omitted.
  • Z 11 represents an electron withdrawing group having a Hammett's substituent constant ⁇ p value of 0.2 or more.
  • the electron-withdrawing group in Z 11 is an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more, preferably 0.30 or more.
  • the upper limit of the sigma p value is preferably 1.0 or less.
  • the electron-withdrawing group having a ⁇ p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy A group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, a heterocyclic group, a halogen atom, an azo group
  • Z 11 is preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and even more preferably a cyano group.
  • the substituent in Z 11 may be further substituted.
  • Z 12 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, a heterocyclic group, or an acyl group. Among these, Z 12 is more preferably an alkyl group. The substituent in Z 12 may be further substituted.
  • R 11 and R 12 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl. Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. However, R 11 and R 12 do not represent a hydrogen atom at the same time.
  • R 11 and R 12 are each independently a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl Group, a substituted or unsubstituted alkylsulfonyl group, and a substituted or unsubstituted arylsulfonyl group are preferable, and a hydrogen atom, a substituted aryl group, and a substituted heterocyclic group are more preferable, and among them, a substituted aryl group and a substituted heterocyclic group are particularly preferable. .
  • the substituent is a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a straight chain having 2 to 12 carbon atoms, or A branched alkenyl group, a linear or branched alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, sec -Butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), or ionic hydrophilic groups (eg carboxylates (preferably alkali metal salts), Sulfonic acid or sulfonate (preferably al
  • R 13 , R 14 , b, c, and d are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxy group, carbamoyl Group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonyl group substituted with an alkyl group, aryl group
  • R 13 and R 14 are each independently preferably a hydrogen atom, an alkyl group, a cyano group, a carboxy group, a carbamoyl group, or an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, a cyano group, or a carboxy group.
  • Each group may be further substituted, and the substituent is a straight chain or branched alkyl group having 1 to 12 carbon atoms or a straight chain or branched chain having 7 to 18 carbon atoms in the same manner as R 11 and R 12.
  • Aralkyl group straight or branched alkenyl group having 2 to 12 carbon atoms, straight or branched alkynyl group having 2 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms Or an ionic hydrophilic group is preferred.
  • R 13 is a hydrogen atom, preferably when R 14 is an alkyl group having 1 to 6 carbon atoms, R 13 is a hydrogen atom and R 14 is a methyl group is more preferable.
  • B, c, and d are each independently preferably a hydrogen atom, an alkyl group, a cyano group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, or an ionic hydrophilic group, and a hydrogen atom, an alkyl group, a cyano group, An ionic hydrophilic group is more preferable.
  • Each group may be further substituted, and the substituent is a straight chain or branched alkyl group having 1 to 12 carbon atoms or a straight chain or branched chain having 7 to 18 carbon atoms in the same manner as R 11 and R 12.
  • Aralkyl group straight or branched alkenyl group having 2 to 12 carbon atoms, straight or branched alkynyl group having 2 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms Or an ionic hydrophilic group is preferred.
  • c is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • B and d are each independently more preferably a hydrogen atom or an ionic hydrophilic group, a hydrogen atom, a sulfonic acid or a sulfonate (preferably an alkali metal salt), or a carboxylic acid or a carboxylate (preferably Alkali metal salts) are more preferable, and the combination of b and d is particularly preferably a combination of a hydrogen atom and a sulfonic acid or a sulfonate.
  • a and e each independently represents an alkyl group, an alkoxy group, or a halogen atom.
  • a and e both represent an alkyl group, the total carbon number of the alkyl group is 3 or more, and the alkyl in a and e The group may be further substituted.
  • R 13 and R 11 , or R 11 and R 12 may be bonded to each other to form a 5-membered ring or a 6-membered ring.
  • a and b, or e and d may be bonded to each other to form a ring.
  • Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, or a heterocyclic group.
  • the group in Q may have a substituent.
  • Q is preferably an aryl group substituted with an electron-withdrawing group or a heterocyclic group substituted with an electron-withdrawing group.
  • the electron-withdrawing group which is the substituent of Q is preferably a group having a Hammett's substituent constant ⁇ p value of 0.20 or more, and a Hammett's substituent constant ⁇ p value of 0.30 or more. More preferred.
  • the upper limit of the sigma p value is preferably 1.0 or less.
  • electron-withdrawing group having a ⁇ p value of 0.20 or more are the same as Z 11 in the general formula (M), and are sulfonic acid or sulfonate (preferably alkali metal salt), carboxylic acid or Carboxylic acid salts (preferably alkali metal salts) are preferred.
  • Z 11 is an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more, preferably 0.30 or more.
  • the upper limit of the sigma p value is preferably 1.0 or less.
  • Z 11 is more preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a cyano group.
  • Z 12 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, and more preferably an alkyl group. Each substituent may be further substituted. More specifically, the alkyl group as Z 12 includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, excluding the carbon atoms of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • substituents examples include a hydroxy group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.
  • substituents include a hydroxy group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.
  • Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group. Each of these substituents may be further substituted. Furthermore, Q is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group.
  • the electron-withdrawing group serving as the substituent for Q is an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more, preferably 0.30 or more. The upper limit of the sigma p value is preferably 1.0 or less.
  • a heterocyclic group substituted with an electron-withdrawing group is preferred, a sulfo group, a substituted or unsubstituted carbamoyl group, a benzoxazole ring substituted with a substituted or unsubstituted sulfamoyl group, and a benzothiazole ring are preferred, A benzothiazole ring substituted with a sulfo group or a substituted sulfamoyl group is particularly preferred.
  • a and e are preferably an alkyl group or a halogen atom, and when both a and e are alkyl groups, they are unsubstituted alkyl groups, and the total number of carbon atoms of a and e is 3 or more (preferably 5 or less).
  • A, b, c and d are each independently a hydrogen atom, a halogen atom, an alkyl group, an ionic hydrophilic group (preferably each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ionic group) The case of a hydrophilic group) is preferred.
  • c is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.
  • b and d are each independently preferably a hydrogen atom or an ionic hydrophilic group, more preferably a hydrogen atom, a sulfo group or a carboxy group, and further preferably a combination of b and d is a hydrogen atom and a sulfo group.
  • R 13 is a hydrogen atom
  • R 14 is an alkyl group (particularly a methyl group).
  • R 11 and R 12 are each independently a hydrogen atom, a substituted aryl group, or a substituted heterocyclic group.
  • the compound represented by the general formula (M) has at least one ionic hydrophilic group (preferably 3 or more and 6 or less) in the molecule. That is, in the general formula (M), at least one of Z 11 , Z 12 , R 11 , R 12 , R 13 , R 14 , a, b, c, d, e and Q is at least one ionic hydrophilic Has a sex group.
  • the ionic hydrophilic group includes a sulfonic acid group (sulfo group), a carboxylic acid group (carboxy group), a phosphonic acid group (phosphono group), a quaternary ammonium group, and the like.
  • a carboxy group, a phosphono group, and a sulfo group are preferable, and among them, a carboxy group and a sulfo group are preferable. In particular, at least one is most preferably a sulfo group.
  • the carboxy group, phosphono group and sulfo group may be in the form of a salt.
  • counter ions forming the salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).
  • alkali metal salts are preferable.
  • alkali metal salts potassium ion, sodium ion and lithium ion are preferable, and lithium ion is most preferable.
  • a combination of an ionic hydrophilic group being a sulfo group and a counter ion being lithium ion is most preferable from the viewpoint of improving solubility and suppressing bronzing during ink jet recording.
  • the compound represented by the general formula (M) preferably has 3 or more and 6 or less ionic hydrophilic groups in the molecule, more preferably 3 or more and 6 or less sulfo groups, and a sulfo group More preferably, the number is 3 or more and 5 or less.
  • R 1 , R 5 , R 6 , and R 10 each independently represents an alkyl group.
  • R 2 , R 3 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom or Represents a substituent.
  • M 1 and M 2 each independently represents a hydrogen atom, an alkali metal ion or an ammonium ion.
  • R 1 , R 5 , R 6 , and R 10 in the general formula (MM) each independently represent an alkyl group.
  • alkyl having 1 to 6 carbon atoms It preferably represents a group, more preferably represents an alkyl group having 1 to 3 carbon atoms, more preferably represents a methyl group, an ethyl group, or an isopropyl group, and particularly preferably represents a methyl group.
  • the alkyl group represented by R 1 , R 5 , R 6 and R 10 may have a substituent, and examples of the substituent include a substituent selected from the following substituent group A.
  • R 3 and R 8 in the general formula (MM) represent a substituent examples include substituents selected from the following substituent group A, and among them, an alkyl group is preferable.
  • R 3 and R 8 represent an alkyl group from the viewpoint of availability of raw materials and ease of synthesis, it is more preferable to represent an alkyl group having 1 to 3 carbon atoms, and a methyl group, an ethyl group, or an isopropyl group More preferably, it represents a methyl group.
  • R 2 and R 7 in the general formula (MM) represent a substituent
  • R 2 and R 7 in the general formula (MM) preferably each independently represent a hydrogen atom or an alkyl group, and more preferably represent a hydrogen atom from the viewpoint of availability of raw materials and ease of synthesis.
  • R 2 , R 3 , R 7 and R 8 in the general formula (MM) represent an alkyl group
  • the alkyl group may have a substituent, and examples of the substituent include the following substituent group A
  • the substituent selected from is mentioned.
  • R ⁇ 11 >, R ⁇ 12 >, R ⁇ 13> , R ⁇ 14> , R ⁇ 15> , R ⁇ 16> , R ⁇ 17> , R ⁇ 18> , R ⁇ 19>, and R ⁇ 20 > each independently represents a hydrogen atom or a substituent.
  • substituents include a substituent selected from the above substituent group A.
  • R 11 and R 16 each independently preferably represents a hydrogen atom, a hydroxy group, a chlorine atom or a methyl group, more preferably a hydrogen atom, a hydroxy group or a methyl group, and more preferably a hydrogen atom or a hydroxy group Is more preferable, and a hydroxy group is particularly preferable.
  • R 12 , R 14 , R 17 and R 19 each independently preferably represent a hydrogen atom or an ionic hydrophilic group, and are a hydrogen atom, a carboxy group, a carboxy group salt, a sulfo group, or a sulfo group salt. Is more preferably represented, a hydrogen atom or a carboxy group or a salt thereof is more preferred, and a carboxy group or a salt thereof is particularly preferred.
  • the salt an alkali metal or alkaline earth metal salt is preferable, and an alkali metal salt is more preferable. Examples of the alkali metal include lithium, potassium, and sodium.
  • R 13 and R 18 preferably each independently represent a hydrogen atom or an ionic hydrophilic group, more preferably a hydrogen atom or a carboxy group, still more preferably a hydrogen atom, and R 13 and R 18 are It is particularly preferred that both represent a hydrogen atom.
  • the compound represented by the general formula (MM) preferably satisfies at least one of the following conditions (i-1) and (i-2), and the following conditions (i-1) and (i-2) It is more preferable to satisfy both.
  • Condition (i-1) At least one of R 11 , R 12 , R 13 , R 14 , and R 15 represents a carboxy group or a salt thereof.
  • the compound represented by the general formula (MM) preferably satisfies at least one of the following conditions (ii-1) and (ii-2), and the compounds represented by the following conditions (ii-1) and (ii-2) It is more preferable to satisfy both.
  • Condition (ii-1) At least one of R 11 , R 12 , R 13 , R 14 , and R 15 represents a hydroxy group, and at least one represents a carboxy group or a salt thereof.
  • R 11 , R 12 , R 13 , R 14 , and R 15 represent a carboxy group or a salt thereof.
  • R 16 , R 17 , R 18 , R 19 and R 20 represent a carboxy group or a salt thereof.
  • R 11 represents a hydroxy group
  • R 12 and R 14 represent a carboxy group or a salt thereof
  • R 13 and R 15 represent a hydrogen atom
  • R 16 represents a hydroxy group
  • R 17 and R 19 represent carboxy.
  • R 18 and R 20 represent a hydrogen atom.
  • M 1 and M 2 in the general formula (MM) each independently represent a hydrogen atom, an alkali metal ion or an ammonium ion, and represent a hydrogen atom, a lithium ion (Li + ), a sodium ion (Na + ), a potassium ion ( K + ) or ammonium ion (NH 4+ ), preferably lithium ion or sodium ion, more preferably lithium ion or a mixed ion mainly composed of lithium ion, lithium Most preferably it represents an ion.
  • R 11 and R 16 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a methyl group.
  • M represents a hydrogen atom, an alkali metal ion, or an ammonium ion.
  • halogen atom in the case where R 11 and R 16 in the general formula (MM-1A) represent a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom or a bromine atom is particularly preferable, and a chlorine atom is most preferable.
  • R 11 and R 16 in the general formula (MM-1A) preferably represent a hydrogen atom, a chlorine atom, a hydroxy group, or a methyl group, more preferably a hydrogen atom or a hydroxy group, and a hydroxy group. Most preferred.
  • a plurality of M each independently represents a hydrogen atom, an alkali metal ion, or an ammonium ion.
  • Each M is preferably independently an alkali metal ion (preferably a lithium ion, a sodium ion, or a potassium ion).
  • a lithium ion or a sodium ion is particularly preferable, and a lithium ion is most preferable.
  • the compound represented by the general formula (MM) can be synthesized by a known method (for example, a method described in International Publication No. 2017/006939).
  • the ratio of the mass of lithium to the total mass of alkali metals in the magenta ink composition is preferably 70% by mass or more, more preferably 75% by mass or more, and still more preferably 80% by mass or more.
  • the ratio of the mass of lithium is 70% by mass or more, the thickening phenomenon when mixed with an ink composition other than the magenta ink composition (especially the yellow ink composition) is effectively suppressed. As a result, it is possible to suppress ink stains on the recording medium caused by the accumulation of the ink composition.
  • the magenta ink composition in the present disclosure contains solvent A, solvent B, solvent C, and solvent D.
  • Preferred solvents in the magenta ink composition are the same as those of the preferred solvent in the yellow ink composition.
  • the solvent A is 2-ethyl-1,3-hexanediol
  • the solvent B is 2-pyrrolidone.
  • An embodiment in which the solvent C is 1,3-butanediol and the solvent D is glycerin is preferable.
  • the cyan ink composition in the present disclosure includes at least one compound (also referred to as a cyan dye) selected from the group consisting of the compound represented by the general formula (C) and a salt thereof, and the solvent A.
  • Solvent B, solvent C, solvent D, and water and may further contain other components such as surfactants and additives as necessary.
  • the solvent A, the solvent B, the solvent C, the solvent D, and water in the cyan ink composition are synonymous with those in the above-described yellow ink composition, and preferred embodiments are also the same. Therefore, detailed description in this column is omitted.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, Alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino Group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamo
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, Hydroxy group, nitro group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphoryl group, acyl group or ionic hydrophilic group are preferred, hydrogen atom, halogen atom, cyano group, A hydroxy group, a sulfamoyl group, a sulfinyl group, a sulfonyl group, and an ionic hydrophilic group are more preferable, and a hydrogen atom is still more preferable.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, and each group further represents a substituent. You may have. At least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
  • Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group
  • a substituted heterocyclic group more preferably a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group, and still more preferably a substituted alkyl group.
  • l, m, n, p, q1, q2, q3 and q4 each independently represent an integer of 1 or 2.
  • M represents a metal atom or a metal oxide, hydroxide or halide.
  • metal atoms in M Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like.
  • the oxide include VO and GeO.
  • the hydroxide include Si (OH) 2 Cr (OH) 2 and Sn (OH) 2 .
  • the halides AlCl, SiCl 2, VCl, VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.
  • Cu, Ni, Zn, and Al are preferable, and Cu is more preferable.
  • Pc phthalocyanine ring
  • L a divalent linking group
  • M may be the same or different.
  • the divalent linking group represented by L includes an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO 2 —), an imino group (—NH —), A methylene group (—CH 2 —), and a group obtained by combining at least two of these are preferable.
  • a compound selected from the group consisting of a compound represented by the following general formula (C-1) and a salt thereof is preferable.
  • Z 1 , Z 2 , Z 3 , Z 4 , 1, m, n, p and M are the same as Z 1 , Z 2 , Z 3 , Z 4 in the general formula (C). , L, m, n, p and M.
  • n and p are each independently an integer of 1 or 2.
  • Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group
  • a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, and a substituted alkyl group is more preferable.
  • Z 1 , Z 2 , Z 3 , and Z 4 are each independently Z 11 (Z 11 represents — (CH 2 ) 3 SO 3 M 2 , M 2 represents an alkali metal atom), and / or Or Z 12 (Z 12 represents — (CH 2 ) 3 SO 2 NHCH 2 CH (OH) CH 3 ), and is particularly contained in the whole cyan dye represented by the general formula (C-1).
  • at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
  • M 2 is preferably an alkali metal atom, more preferably a lithium, sodium, or potassium ion, and even more preferably a lithium ion.
  • M is synonymous with M in the general formula (C), and preferred embodiments are also the same.
  • the ratio of the mass of lithium to the total mass of alkali metals in the cyan ink composition is preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, 90 A mass% or more is particularly preferred.
  • the ratio of the mass of lithium is 70% by mass or more, the thickening phenomenon when mixed with an ink composition other than the cyan ink composition (particularly the yellow ink composition) is effectively suppressed. As a result, it is possible to suppress ink stains on the recording medium caused by the accumulation of the ink composition.
  • the cyan ink composition in the present disclosure contains solvent A, solvent B, solvent C, and solvent D.
  • the preferred solvent in the cyan ink composition is the same as the preferred combination of solvents in the yellow ink composition.
  • the solvent A is 2-ethyl-1,3-hexanediol
  • the solvent B is 2-pyrrolidone.
  • An embodiment in which the solvent C is 1,3-butanediol and the solvent D is glycerin is preferable.
  • the black ink composition in the present disclosure includes at least one compound selected from the group consisting of the compound represented by the general formula (B) and a salt thereof (also referred to as a black dye), and the solvent A. In addition, it preferably contains at least one compound selected from the group consisting of a compound represented by formula (B-1) and a salt thereof, which contains solvent B, solvent C and solvent D, and water. .
  • the black ink composition may further contain other components such as a surfactant and an additive as necessary.
  • the solvent A, the solvent B, the solvent C, the solvent D, and water in the black ink composition are synonymous with those in the above-described yellow ink composition, and preferred embodiments are also the same. Therefore, detailed description in this column is omitted.
  • JP-A-2007-138124 For the details of the general formula (B), the description in paragraphs 0690-0764, paragraphs 0673-0687, etc. of JP-A-2007-138124 can be referred to.
  • A represents an aromatic group that may be substituted or a heterocyclic group that may be substituted.
  • X represents a nitrogen atom or ⁇ C (W 1 ) —
  • W 1 represents an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more.
  • V 1 , W, R 43 , and R 44 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, or a carbamoyl group.
  • R 41 and R 42 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent.
  • R 41 and R 42 do not represent a hydrogen atom at the same time.
  • R 43 and R 41 , or R 41 and R 42 may be bonded to each other to form a 5-membered ring or a 6-membered ring.
  • R 11 and R 12 each independently represents an ionic hydrophilic group, preferably a sulfo group and a salt of a sulfo group, a salt of a carboxy group and a carboxy group, and more Preferably, it is a sulfo group.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy Group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salt), carboxy group (including salt) ), Hydroxyl group (may be a salt), phosphono group (may be a salt) or quaternary ammonium, among which a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including a salt), a carboxy group (including a)
  • (B) W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And is preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted ⁇ -naphthyl group, a pyridine ring or a thiazole ring.
  • R 41 and R 42 are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or an arylsulfonyl group, and a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are more preferable, and an aryl group having a hydrogen atom and a substituent is particularly preferable.
  • R 41 and R 42 are not simultaneously hydrogen atoms.
  • R 43 and R 41 , or R 41 and R 42 may be bonded to each other to form a 5-membered to 6-membered ring.
  • R 43 and R 44 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxy group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonyl An amino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, or a heterocyclic sulfonylamino group is represented.
  • R 43 is preferably a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, preferably a cyano group, a carboxy group, A carbamoyl group and an alkoxycarbonyl group are more preferable, and a cyano group is still more preferable.
  • R 44 includes a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, and an amino group (an alkylamino group, an arylamino group, and a heterocyclic amino group).
  • R 45 and R 46 are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or an arylsulfonyl group, and further a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring.
  • a group is preferable, and a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and a hydrogen atom and an aryl group having a substituent are most preferable.
  • R 45 and R 46 are not simultaneously hydrogen atoms.
  • R 45 and R 46 may combine to form a 5- to 6-membered ring.
  • W represents a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring group, a thiophene ring group, an imidazole ring group, a thiazole ring group, a benzothiazole ring group, a pyridine ring group).
  • a substituted phenyl group for example, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring group, a thiophene ring group, an imidazole ring group, a thiazole ring group, a benzothiazole ring group, a pyridine ring group).
  • a pyridazine ring group is preferred, and a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted ⁇ -naphthyl group, a pyridine ring or a thiazole ring is more preferred.
  • R 11 and R 12 each independently represents an ionic hydrophilic group, preferably a sulfo group (including a salt) or a carboxy group (including a salt), and more preferably a sulfo group.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy Group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salt), carboxy group (including salt) ), Hydroxyl group (may be salt), phosphono group (may be salt) or quaternary ammonium, hydrogen atom, halogen atom, alkyl group, sulfo group (including salt), carboxy group (including salt), hydroxyl group (including salt) may also be) is preferably a hydrogen
  • (B) W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring group, a thiophene ring group, an imidazole ring group, a thiazole ring group, a benzothiazole ring group, A pyridine ring group or a pyridazine ring group), and a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted ⁇ -naphthyl group, a pyridine ring or a thiazole ring is preferred.
  • a substituted or unsubstituted naphthyl group for example, a pyrrole ring group, a thiophene ring group, an imidazole ring group, a thiazole ring group
  • W 11 represents an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more, preferably an electron-withdrawing group having a ⁇ p value of 0.30 or more, and an electron of 0.45 or more An attractive group is more preferable, and an electron attractive group of 0.60 or more is still more preferable. It is desirable that the ⁇ p value does not exceed 1.0.
  • W 11 is an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms.
  • a 20 arylsulfonyl group, a carbamoyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to 20 carbon atoms are preferable, and a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and a 6 to 6 carbon atom are more preferable.
  • R 41 and R 42 are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or an arylsulfonyl group, and a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are more preferable, and an aryl group having a hydrogen atom and a substituent is particularly preferable.
  • R 41 and R 42 are not simultaneously hydrogen atoms.
  • R 43 and R 41 , or R 41 and R 42 may be bonded to each other to form a 5-membered to 6-membered ring.
  • R 43 and R 44 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxy group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonyl An amino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, and a heterocyclic sulfonylamino group are represented.
  • R 43 is preferably a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, preferably a cyano group, a carboxy group, A carbamoyl group and an alkoxycarbonyl group are more preferable, and a cyano group is still more preferable.
  • R 44 includes a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, and an amino group (an alkylamino group, an arylamino group, and a heterocyclic amino group).
  • R 45 and R 46 are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or an arylsulfonyl group, and a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are more preferable, and an aryl group having a hydrogen atom and a substituent is particularly preferable.
  • R 45 and R 46 are not simultaneously hydrogen atoms.
  • R 45 and R 46 may combine to form a 5- to 6-membered ring.
  • the black ink composition preferably further contains a compound represented by the following general formula (BA).
  • BA general formula
  • the black color can be adjusted.
  • a ring, B ring, and C ring each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
  • Q 1 and Q 2 are each independently a hydrogen atom, ionic hydrophilic group, halogen atom, cyano group, nitro group, substituted or unsubstituted acylamino group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted Alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted It represents a substituted sulfamoyl group, a substituted or unsub
  • L 12 represents a divalent linking group, and is preferably a carbonyl group or a substituted or unsubstituted heterocyclic group (for example, a substituted or unsubstituted triazine ring group).
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 11 , A 12 , A 13 , A 14 , A 15 , B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 11 , B 12 , B 13 , B 14 , B 15 , B 16 , C 1 , C 2 , C 3 , C 4 , C 11 , C 12 , C 13 , and C 14 are each independently a hydrogen atom, ion Hydrophilic group, halogen atom, cyano group, nitro group, substituted or unsubstituted acylamino group, substituted or unsubstituted sulfonylamino group, substituted or unsubsti
  • an ionic hydrophilic group More preferred is an ionic hydrophilic group.
  • a sulfo group (including a salt) and a carboxy group (including a salt) are preferable, and a sulfo group is more preferable.
  • the above-mentioned A 1 to A 5 , A 11 to A 15 , B 1 to B 6 , B 11 to B 16 , C 1 to C 4 , C 11 to C 14 , Q 1 , Q 2 , and L 12 At least one has at least one ionic hydrophilic group.
  • BA-1 and BA-2) of the compound represented by the general formula (BA) and salts thereof are shown below. However, the present disclosure is not limited to the specific examples shown below.
  • the ratio of the mass of lithium to the total mass of alkali metals in the black ink composition is preferably 70% by mass or more, and more preferably 75% by mass or more.
  • the ratio of the mass of lithium is 70% by mass or more, the thickening phenomenon when mixed with an ink composition other than the black ink composition (particularly the yellow ink composition) is effectively suppressed. As a result, it is possible to suppress ink stains on the recording medium caused by the accumulation of the ink composition.
  • the black ink composition in the present disclosure contains solvent A, solvent B, solvent C, and solvent D.
  • the preferred solvent in the black ink composition is the same as the preferred combination of solvents in the yellow ink composition.
  • the solvent A is 2-ethyl-1,3-hexanediol
  • the solvent B is 2-pyrrolidone.
  • An embodiment in which the solvent C is 1,3-butanediol and the solvent D is glycerin is preferable.
  • the physical properties of the yellow ink composition, cyan ink composition, magenta ink composition and black ink composition in the present disclosure are not particularly limited, but preferably have the following physical properties.
  • the yellow ink composition, cyan ink composition, magenta ink composition and black ink composition in the present disclosure preferably have a pH at 25 ° C. ( ⁇ 1 ° C.) of 6.5 to 11, preferably 7.0 to 10.5. More preferred.
  • the viscosity at 25 ° C. ( ⁇ 1 ° C.) of the yellow ink composition, cyan ink composition, magenta ink composition and black ink composition in the present disclosure is preferably in the range of 6 mPa ⁇ s to 10 mPa ⁇ s, and 7 mPa ⁇ s. The range of ⁇ 9 mPa ⁇ s is more preferable.
  • the viscosity is measured under the condition of 25 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
  • the surface tension at 25 ° C. ( ⁇ 1 ° C.) of the yellow ink composition, cyan ink composition, magenta ink composition and black ink composition in the present disclosure is preferably 60 mN / m or less, preferably 30 mN / m ⁇ More preferably, it is 50 mN / m, and even more preferably 35 mN / m to 45 mN / m.
  • the surface tension is measured at 25 ° C. by a plate method using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • the yellow ink composition As a method for preparing the yellow ink composition, the cyan ink composition, the magenta ink composition, and the black ink composition in the present disclosure, for example, various components contained in the ink composition are mixed to maintain good uniformity.
  • the ink composition in the present disclosure is not limited to the above method.
  • the ink jet recording method of the present disclosure records an image using the ink set of the present disclosure described above.
  • the ink jet recording method is a method in which an ink composition is ejected as droplets from a thin nozzle, and the ejected droplets are attached to a recording medium.
  • a method a method using an electrostatic suction method, a method in which pressure and mechanical vibration are applied to the ink composition and discharging, a method in which a piezoelectric element is used, and the ink composition is heated by an electrode according to print signal information. Examples thereof include a method utilizing foaming and foam expansion.
  • Example 1 [Preparation of Yellow Ink-1] Components in the following composition were mixed to prepare yellow ink-1.
  • Sodium bicarbonate 0.01% by mass ⁇ Proxel GXL: 0.03 mass% (Arch Chemicals Japan KK; antiseptic)
  • Ion-exchanged water Remaining amount when 100% by mass as a whole
  • the YELLOW-1 dye which is a Li salt
  • Li salt was obtained by changing KOH at the time of making a potassium hydroxide (KOH) aqueous solution, which is a 10% by mass aqueous solution of the obtained crystal, to lithium hydroxide (LiOH).
  • KOH potassium hydroxide
  • LiOH lithium hydroxide
  • magenta ink-1 Components in the following composition were mixed to prepare magenta ink-1.
  • -Magenta ink-1 composition- ⁇ MAGENTA-1 4.0% by mass ⁇ 2-ethyl-1,3-hexanediol (solvent A): 2.0% by mass ⁇ 2-Amino-2-ethyl-1,3-propanediol (solvent B) ...
  • Viscosity increase during ink mixing Five 50-ml gas bottles are prepared, 30 g of each of the four types of ink and mixed ink are put in separate gas bottles, and the opening of the gas bottle is opened without a cap. In this state, it was left for 4 days under conditions of a temperature of 45 ° C. and a humidity of 20% RH. After standing, the viscosity (unit: mPa ⁇ s) of each ink and mixed ink was measured at 25 ° C. The viscosity was measured using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
  • the measured values of the viscosity of each of the four color inks after being left alone were averaged, and the ratio of the viscosity of the mixed ink after being left to the average value was calculated to obtain a percentage (%).
  • the percentage value obtained here was defined as the thickening rate (%) of the viscosity of the ink that increases when a plurality of types of ink are mixed. It is considered that the higher the viscosity increase rate, the more easily fine precipitation occurs from the mixed ink during drying and concentration, and the viscosity increases.
  • YELLOW-1, 2, 4 and 5 in the above table show specific examples of the yellow dye described above.
  • the numerical value in the parenthesis in the column of the solvent in the table represents the SP value (unit: MPa 1/2 ) measured by the method described above.
  • the ratio of the total mass of lithium to the total mass of alkali metals when all the inks are mixed at an equal mass ratio is 70% by mass or more.
  • the increase rate (thickening rate) of the ink viscosity when a plurality of inks are mixed is kept low, and ink stains on the back surface and the side surface corresponding to the thickness of the recording medium are reduced compared to the comparative example. It was.
  • the ratio of the total mass of lithium to the total mass of alkali metals is more preferably 80% by mass or more, and 85% by mass. The above is more preferable.
  • the rate of increase in the viscosity of the ink when the ink was mixed was remarkable, and as a result, the ink smears were remarkable.
  • Example 2 In Example 1, magenta ink-1, cyan ink-1, and black ink-1, except that the type of dye and the type and content of the solvent were changed as shown in Table 6, Magenta ink-2, magenta ink-3, cyan ink-2, cyan ink-3, black ink-2, and black ink-3 were prepared in the same manner as cyan ink-1 or black ink-1. The alkali metal content contained in each ink was determined in the same manner as in Example 1. Table 6 shows the measurement results.
  • MAGENTA-2,4, CYAN-2,4, and BLACK-2,3 in the above table indicate specific examples of the magenta dye, the specific example of the cyan dye, and the specific example of the black dye, respectively.
  • magenta ink-1 is replaced with magenta ink-2 or magenta ink-3
  • cyan ink-1 is replaced with cyan ink-2 or cyan ink-3
  • black ink-1 is replaced with black ink-2 or black ink-3.
  • the viscosity increase rate (%) and ink smear when ink was mixed were evaluated in the same manner as in Example 1.
  • Table 7 shows the evaluation results. Also, cations were measured in the same manner as in Example 1 for the prepared magenta ink-2, magenta ink-3, cyan ink-2, cyan ink-3, black ink-2, and black ink-3. And the ratio of the mass of lithium to the total mass of alkali metal was determined.
  • the ratio of the total mass of lithium to the total mass of alkali metals when all the inks are mixed at an equal mass ratio is adjusted to 80% by mass or more.
  • the rate of increase in viscosity (thickening rate) of the ink when a plurality of inks are mixed is suppressed, and ink stains on the back surface and the side surface corresponding to the thickness of the recording medium are reduced compared to the comparative example.
  • the ratio of the total mass of lithium to the total mass of alkali metals is more preferably 80% by mass or more, and 85% by mass. The above is more preferable.
  • the rate of increase in the viscosity of the ink when the ink was mixed was remarkable, and as a result, the ink smears were remarkable.
  • Example 3 Magenta ink-4 and magenta ink-5 were prepared in the same manner as magenta ink-1, except that only the dye type of magenta ink-1 was changed as shown in Table 8. Further, the content of alkali metal contained in each ink was determined in the same manner as in Example 1. Table 8 shows the measurement results.
  • the ratio of the total mass of lithium to the total mass of alkali metals when the ink represented by the general formula (MM) was mixed at an equal mass ratio was adjusted to 80% by mass or more.
  • the rate of increase in the viscosity of the ink was suppressed, and ink stains were further reduced.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
PCT/JP2019/003421 2018-01-31 2019-01-31 インクセット及びインクジェット記録方法 WO2019151412A1 (ja)

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CN201980010408.8A CN111684026B (zh) 2018-01-31 2019-01-31 油墨组及喷墨记录方法
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CN116057136A (zh) * 2020-07-29 2023-05-02 兰达公司 喷墨油墨制剂及其用途

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138124A (ja) 2005-10-20 2007-06-07 Fujifilm Corp インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法、記録物及び褪色改良方法
JP2008101173A (ja) * 2006-10-20 2008-05-01 Fujifilm Corp インク、インクセット及びインクジェット記録方法
JP2009132891A (ja) * 2007-10-31 2009-06-18 Fujifilm Corp インクセット、インクジェット記録方法、及び記録物
JP2009226642A (ja) * 2008-03-19 2009-10-08 Fujifilm Corp インクジェット画像の形成方法
JP2011202117A (ja) 2010-03-26 2011-10-13 Fujifilm Corp インク組成物、インクセット、および画像形成方法
JP2012072373A (ja) * 2010-08-31 2012-04-12 Fujifilm Corp インク
JP2012149220A (ja) * 2010-12-28 2012-08-09 Fujifilm Corp インク組成物、インクジェット記録用インク及びインクジェット記録方法
JP2012188545A (ja) 2011-03-10 2012-10-04 Ricoh Co Ltd インクジェット記録用インクセット、並びにインクカートリッジ、インクジェット記録方法、インクジェット記録装置及びインク記録物
JP2012193330A (ja) 2011-02-28 2012-10-11 Fujifilm Corp インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法及び記録物
JP2012193331A (ja) * 2011-02-28 2012-10-11 Fujifilm Corp インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法及び記録物
JP2012193329A (ja) * 2011-02-28 2012-10-11 Fujifilm Corp インク組成物、インクジェット記録用インク及びインクジェット記録方法
JP2013001854A (ja) 2011-06-17 2013-01-07 Fujifilm Corp インクセット及び画像形成方法
JP2016029148A (ja) * 2014-07-24 2016-03-03 セイコーエプソン株式会社 インクセット
WO2017006939A1 (ja) 2015-07-09 2017-01-12 富士フイルム株式会社 化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物
JP2018015912A (ja) 2016-07-25 2018-02-01 富士ゼロックス株式会社 画像処理装置、画像処理システム及び画像処理プログラム

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10108601A1 (de) * 2001-02-22 2002-09-05 Basf Ag Thermochrome Rylenfarbstoffe
JP4863418B2 (ja) * 2001-07-06 2012-01-25 株式会社リコー インクジェット記録用インク、カラーインクセット及び画像の形成方法
US7229166B2 (en) * 2003-08-11 2007-06-12 Canon Kabushiki Kaisha Image-forming method, image-forming apparatus, ink set, and ink
KR101170372B1 (ko) * 2004-07-13 2012-08-01 후지필름 가부시키가이샤 블랙잉크 조성물, 이것을 포함하는 잉크셋, 및 잉크젯기록방법
KR101003816B1 (ko) * 2005-10-20 2010-12-28 가부시키가이샤 리코 기록용 잉크, 기록용 매체, 잉크 매체 세트, 잉크 기록물,잉크젯 기록 방법 및 잉크젯 기록 장치
JP5022689B2 (ja) * 2006-01-24 2012-09-12 富士フイルム株式会社 インク組成物、インクセットおよび記録方法
JP4465721B2 (ja) * 2006-09-29 2010-05-19 セイコーエプソン株式会社 インクセット、インクカートリッジ、インクジェット記録方法及び記録物
JP4457412B2 (ja) * 2006-12-14 2010-04-28 セイコーエプソン株式会社 インクセット、インクカートリッジ、インクジェット記録方法及び記録物
DE102007005795A1 (de) * 2007-02-06 2008-08-07 Dystar Textilfarben Gmbh & Co. Deutschland Kg Mischungen von faserreaktiven Azofarbstoffen
JP4390290B2 (ja) * 2007-08-10 2009-12-24 キヤノン株式会社 インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
CN103160226A (zh) * 2011-12-18 2013-06-19 日东电工（上海松江）有限公司 压敏粘合剂组合物、油墨组合物以及利用这些组合物制造的压敏胶带
ES2811071T3 (es) * 2012-05-02 2021-03-10 Lubrizol Advanced Mat Inc Composición dispersante aromática
JP6221439B2 (ja) * 2013-07-11 2017-11-01 株式会社リコー インクジェット記録用インク、インクセット、及びインクジェット記録装置
JP2017088710A (ja) * 2015-11-06 2017-05-25 株式会社リコー インクセット、インクカートリッジ、インクジェット記録方法、及びインクジェット記録装置

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4977371B2 (ja) 2005-10-20 2012-07-18 富士フイルム株式会社 インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法、記録物及び褪色改良方法
JP2007138124A (ja) 2005-10-20 2007-06-07 Fujifilm Corp インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法、記録物及び褪色改良方法
JP2008101173A (ja) * 2006-10-20 2008-05-01 Fujifilm Corp インク、インクセット及びインクジェット記録方法
JP2009132891A (ja) * 2007-10-31 2009-06-18 Fujifilm Corp インクセット、インクジェット記録方法、及び記録物
JP2009226642A (ja) * 2008-03-19 2009-10-08 Fujifilm Corp インクジェット画像の形成方法
JP2011202117A (ja) 2010-03-26 2011-10-13 Fujifilm Corp インク組成物、インクセット、および画像形成方法
JP2012072373A (ja) * 2010-08-31 2012-04-12 Fujifilm Corp インク
JP2012149220A (ja) * 2010-12-28 2012-08-09 Fujifilm Corp インク組成物、インクジェット記録用インク及びインクジェット記録方法
JP2012193329A (ja) * 2011-02-28 2012-10-11 Fujifilm Corp インク組成物、インクジェット記録用インク及びインクジェット記録方法
JP2012193330A (ja) 2011-02-28 2012-10-11 Fujifilm Corp インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法及び記録物
JP2012193331A (ja) * 2011-02-28 2012-10-11 Fujifilm Corp インクセット、インクカートリッジ、インクジェットプリンター、インクジェット記録方法及び記録物
JP2012188545A (ja) 2011-03-10 2012-10-04 Ricoh Co Ltd インクジェット記録用インクセット、並びにインクカートリッジ、インクジェット記録方法、インクジェット記録装置及びインク記録物
JP2013001854A (ja) 2011-06-17 2013-01-07 Fujifilm Corp インクセット及び画像形成方法
JP2016029148A (ja) * 2014-07-24 2016-03-03 セイコーエプソン株式会社 インクセット
WO2017006939A1 (ja) 2015-07-09 2017-01-12 富士フイルム株式会社 化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物
JP2018015912A (ja) 2016-07-25 2018-02-01 富士ゼロックス株式会社 画像処理装置、画像処理システム及び画像処理プログラム

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
R. F. FEDORS, POLYMER ENGINEERING SCIENCE, vol. 14, 1974, pages 147 - 154
See also references of EP3747963A4

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